CA2913504A1 - Procede de fluoration de composes halogenures de sulfonyle - Google Patents
Procede de fluoration de composes halogenures de sulfonyle Download PDFInfo
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- CA2913504A1 CA2913504A1 CA2913504A CA2913504A CA2913504A1 CA 2913504 A1 CA2913504 A1 CA 2913504A1 CA 2913504 A CA2913504 A CA 2913504A CA 2913504 A CA2913504 A CA 2913504A CA 2913504 A1 CA2913504 A1 CA 2913504A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
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Abstract
On décrit la préparation d'un composé de formule (I) comportant une fonction -SO2F par réaction d'un composé de formule (II) avec un agent de fluoration choisi parmi l'acide fluorhydrique et un fluorure ionique d'un cation monovalent ou divalent : R-SO2F (I) R'-SO2X (II) Où R est choisi parmi les groupements R1, R2 et R3 : R1 = -CnHaFb avec n=1-10, a+b = 2n+1, b = 1; R2 = -CxHyFz-SO2F avec x = 1-10, y+z = 2x et z = 1; R3 = F-CcHhFf avec c = 1-10; h+f = 2c et f = 1; Où R' est choisi parmi les groupements R'1, R'2 et R'3 suivants : R'1 = -CnHaXb avec n=1-10, a+b = 2n+1, b = 1; R'2 = -CxHyXz-SO2X avec x = 1-10, y+z = 2x et z = 1; R'3 = F-CcHhXf avec c = 1 -10; h+f = 2c et f = 1; F désignant un groupe phényle, X = Cl, Br.The preparation of a compound of formula (I) having an -SO 2 F function is described by reacting a compound of formula (II) with a fluorinating agent selected from hydrofluoric acid and an ionic fluoride of a monovalent cation or divalent: R-SO2F (I) R'-SO2X (II) Where R is chosen from the groups R1, R2 and R3: R1 = -CnHaFb with n = 1-10, a + b = 2n + 1, b = 1 ; R2 = -CxHyFz-SO2F with x = 1-10, y + z = 2x and z = 1; R3 = F-CcHhFf with c = 1-10; h + f = 2c and f = 1; Where R 'is selected from the following groups R'1, R'2 and R'3: R'1 = -CnHaXb with n = 1-10, a + b = 2n + 1, b = 1; R'2 = -CxHyXz-SO2X with x = 1-10, y + z = 2x and z = 1; R'3 = F-CcHhXf with c = 1-10; h + f = 2c and f = 1; F denotes a phenyl group, X = Cl, Br.
Description
Process for fluorinating sulfonyl halide compounds The present invention relates to the field of the fluorination of halogenated compounds, generally of chlorinated compounds, bearing an ¨S02X function where X is a halogen other than fluorine. One subject of the invention is in particular the preparation of compounds of sulfonyl fluoride type such as alkylsulfonyl fluorides or benzylsulfonyl fluorides. More specifically, one subject of the present invention is a process for preparing trifluoromethanesulfonyl fluoride (CF3S02F).
Sulfonyl fluoride compounds are intermediates that are particularly advantageous for the synthesis of sulfonimide compounds and compounds bearing a sulfonic acid function, which are high value-added products.
It is known to prepare compounds of sulfonyl fluoride type and in particular trifluoromethanesulfonyl fluoride by electrofluorination of mesyl fluoride (US 4 927 962) or by fluorination of a trifluorosulfinate of a monovalent cation. These prior processes, even though they result in satisfactory performances, suffer from an implementation that is complex and costly (in the case of electrofluorination) and/or that requires steps to be put in place that involve CMR (carcinogenic, mutagenic and reprotoxic) solvents, in particular DMF.
One objective of the invention is therefore to provide a process for preparing sulfonyl fluoride compounds that makes it possible to avoid the drawbacks of the prior art processes. In particular, one objective of the invention is to propose a simplified process for preparing compounds of sulfonyl fluoride type that is cleaner in terms of toxicity of the chemical agents involved and that is more economical. Another objective of the invention is to propose a non-electrochemical process. Yet other objectives will become apparent on reading the invention that follows.
One subject of the present invention is a non-electrochemical process for preparing a fluorinated compound of formula (I) comprising at least one ¨S02F function, characterized in that the compound of formula (I) is prepared by reacting a compound of formula (II) with at least one fluorinating agent selected from hydrofluoric acid and an ionic fluoride of a monovalent or divalent cation:
R-S02F (I) where R is selected from the following groups R1, R2 and R3:
R1 = -C,HaFb with n=1-10, a+b = 2n+1, b 1; preferably n=1, a = 0, b = 3; Process for fluorinating sulfonyl halide compounds The present invention relates to the field of fluorination of halogenated compounds, of the chlorinated compounds, bearing an ¨S02X function where X is a halogen other than fluorite. One subject of the invention is in particular the preparation of compounds of sulfonyl fluoride type such as alkylsulfonyl fluorides or benzylsulfonyl fluorides. more The subject of the present invention is a process for preparing trifluoromethanesulfonyl fluoride (CF3SO2F).
Sulfonyl fluoride compounds are intermediates that are particularly advantageous for the synthesis of sulfonimide compounds and compounds bearing sulfonic acid function, which are high value-added products.
It is known to prepare compounds of sulfonyl fluoride type and in particular trifluoromethanesulfonyl fluoride by electrofluorination of mesyl fluoride (US 4,927,962) or by fluorination of a trifluorosulfinate of a monovalent cation. These priorities processes, even though they result in satisfactory performances, year implementation that is complex and costly (in the case of electrofluorination) and / or that requires CMR (carcinogenic, mutagenic) and reprotoxic) solvents, in particular DMF.
One objective of the invention is to provide a process for preparing sulfonyl fluoride compounds that makes it possible to avoid the drawbacks of the prior art processes. in particular, one objective of the invention is to propose a simplified process for preparing compounds of sulfonyl fluoride the chemical agents involved and that is more economical. Another objective of the invention is to proposes a electrochemical process. Yet other objectives will become apparent on reading the invention that follows.
One subject of the present invention is a non-electrochemical process for preparing a fluorinated compound of formula (I) comprising at least one ¨S02F function, characterized in compound of formula (I) is prepared by reacting a compound of formula (II) with at least one fluorinating agent selected from hydrofluoric acid and anionic fluoride of a Monovalent gold divalent cation:
R-S02F (I) where R is selected from the following groups R1, R2 and R3:
R1 = -C, HaFb with n = 1-10, a + b = 2n + 1, b 1; preferably n = 1, a = 0, b = 3;
2 R2 = -CxHyFz-S02F with x = 1-10, y+z = 2x and z 1;
R3 = (1)-CcHhFf with c = 1-10; h+f = 2c and f 1; (l) denoting a phenyl group;
R'-S02X (II) where R' is selected from the following groups R'1, R'2 and R'3:
R'1 = -C,1-1,Xb with n=1-10, a+b = 2n+1, b 1;
R'2 = -C3HyX,-S02X with x = 1-10, y+z = 2x and z 1;
R'3 = cl)-CcHhXf with c = 1-10; h+f = 2c and f 1; cl) denoting a phenyl group;
X being a halogen atom selected from chlorine and bromine.
The preparation process according to the invention is a non-electrochemical fluorination process. Electrofluorination processes are therefore excluded from the invention.
In accordance with the process according to the invention, the radicals R1 and R'1 advantageously have a value of n between 1 and 5, very preferably between 1 and 3.
Preferably, n is equal to 1. Preferably, the radicals R1 and R'1 are perhalogenated so that b = 3 and a = 0. The radicals R2 and R'2 advantageously have a value of x between 1 and 5, very preferably between 1 and 3. Preferably, x is equal to 1. The radicals R3 and R'3 advantageously have a value of c between 1 and 5, preferably between 1 and 3.
Preferably, c is equal to 1. The phenyl group ci) present in the radicals R3 and R'3 may be substituted with one or more hydroxyl, alkyl, alcohol, thiol, amide or halogen groups and/or by a group -CxHyX,-S02X with x = 1-10, y+z = 2x and z 1, X being a halogen atom selected from chlorine and bromine.
Very preferably, the radical R of the compound (I) prepared according to the process of the invention is the radical R1 wherein n = 1, a = 0 and b = 3, or n = 1, a = 1, b = 2 or else n = 1, a = 2 and b = 1. The compounds of formula CF3S02F, CHF2S02F and CH2FSO2F are thus respectively prepared from the compounds of formula (II) respectively having the formulae CX3S02X (n = 1, a = 0 and b = 3 in R'1), CHX2S02X (n = 1, a = 1, b = 2 in R'1) and CH2XSO2X (n = 1, a = 2 and b = 1 in R'1), where X is bromine or chlorine, preferably chlorine.
Furthernnore, a non-electrochemical process is described for preparing a fluorinated compound of formula S02F2 characterized in that this compound is prepared by reacting a compound of formula S02X2 with at least one fluorinating agent selected from hydrofluoric 2 R2 = -CxHyFz-SO2F with x = 1-10, y + z = 2x and z1;
R3 = (1) -CcHhFf with c = 1-10; h + f = 2c and f 1; (l) denoting a phenyl group;
R'-S02X (II) where R 'is selected from the following groups R'1, R'2 and R'3:
R'1 = -C, 1-1, Xb where n = 1-10, a + b = 2n + 1, b 1;
R'2 = -C3HyX, -SO2X with x = 1-10, y + z = 2x and z1;
R'3 = cl) -CcHhXf with c = 1-10; h + f = 2c and f 1; (cl) denoting a phenyl group;
X being a halogen atom selected from chlorine and bromine.
The preparation process according to the invention is a non-electrochemical fluorination process. Electrofluorination processes are therefore excluded from invention.
In accordance with the process according to the invention, the radicals R1 and R'1 advantageously have a value of n between 1 and 5, very much between 1 and 3.
Preferably, n is equal to 1. Preferably, the radicals R1 and R'1 are perhalogenated so that b = 3 and a = 0. The radicals R2 and R'2 advantageously have a value of x between 1 and 5, very preferred between 1 and 3. Preferably, x is equal to 1. The radicals R3 and R'3 advantageously have a value of between 1 and 5, preferably between 1 and 3.
Preferably, c is equal to 1. The phenyl group ci) present in the radicals R3 and R'3 may be substituted with one or more hydroxyl, alkyl, alcohol, thiol, amide or halogen groups and / or by a group -CxHyX, -S02X with x = 1-10, y + z = 2x and z 1, X being a halogen atom selected from chlorine and bromine.
Very preferably, the radical R of the compound (I) process of the is the radical R1 where n = 1, a = 0 and b = 3, or n = 1, a = 1, b = 2 or else n = 1, a = 2 and b = 1. The compounds of formula CF3S02F, CHF2S02F and CH2FSO2F are THUS
prepared with the compounds of formula (II) the formulae CX3SO2X (n = 1, a = 0 and b = 3 in R'1), CHX2SO2X (n = 1, a = 1, b = 2 in R'1) and CH2XSO2X (n = 1, a = 2 and b = 1 in R'1), where X is bromine or chlorine, preferably chlorine.
Furthernnore, a non-electrochemical process fluorinated compound of formula S02F2 reacting a compound of formula S02X2 with at least one fluorinating agent selected from hydrofluoric
3 acid and an ionic fluoride of a monovalent or divalent cation, X being a halogen atom selected from chlorine and bromine.
The process according to the invention can be carried out in the gas phase or in the liquid phase. Preferably, said process is carried out in the gas phase.
According to the preferred embodiment of the process of the invention, according to which it is carried out in the gas phase, the fluorinating agent used for reacting with the compound of formula (II) is hydrofluoric acid.
The preparation process according to the invention, carried out in the gas phase in the presence of hydrofluoric acid, uses at least one fluorination catalyst. Said fluorination catalyst, used in the gas phase fluorination process, is in particular selected from the catalysts comprising, or consisting of, chromium, zinc, nickel, a mixture of chromium and zinc or a mixture of chromium and nickel.
The fluorination catalyst may in particular be a chromium-based catalyst. The catalyst used is a bulk chromium oxide (that is to say a catalyst comprising only the metallic element and oxygen) or preferably comprises oxides, halides, oxyhalides or minerai salts of chromium, optionally doped with a metallic element such as for example nickel, cobalt, magnesium and zinc. It is preferably a chromium oxide, a chromium fluoride or a chromium oxyfluoride, which may optionally be doped with a metallic element, for example nickel or zinc.
The fluorination catalyst may be subjected to an activation via a heat treatment. In particular, the activation may take place during the fluorination process. The temperature is advantageously chosen between 100 C and 400 C, preferably between 200 C and 300 C.
Use is in particular made of chromium in the form of oxides with different degrees of oxidation and/or in the form of hydroxides in powder or gel form.
It is possible to use an activated chromium(III) oxide prepared, for example, by precipitation of water-soluble chromium(III) salts, such as, for example, chlorides, nitrates, acetates or sulfates, using an aqueous solution of ammonium hydroxide or using an aqueous solution of an alkali metal hydroxide, preferably sodium or potassium hydroxide. The precipitate is dried at around 110 C and calcined at a temperature below 700 C, preferably between 200 C and 600 C. Chromium(III) is understood to mean chromium in the (III) oxidation state.
Anhydrous chromium oxide may be obtained by calcination of inorganic chromium salts, such as ammonium chromate or chromium nitrate, or by calcination of organic chromium salts, such as, for example, chromium oxalates or formates, at a temperature between 200 C
and 500 C, preferably between 250 C and 450 C, and more preferably stil!
between 250 C
and 400 C, under a nitrogen atmosphere. 3 acid and anionic fluoride of a monovalent or divalent cation, X being a halogen atom selected from chlorine and bromine.
The process according to the invention can be carried out in the gas phase in the liquid phase. Preferably, this process is carried out in the gas phase.
According to the preferred embodiment of the process of the invention, according to which it is carried out in the gas phase, the fluorinating agent used for reacting with the compound of formula (II) is hydrofluoric acid.
The preparation process according to the invention, carried out in the gas phase in the presence of hydrofluoric acid, uses at least one fluorination catalyst. Said fluorination catalyst, used in the gas phase fluorination process, is in particular selected from the catalysts comprising, or consisting of, chromium, zinc, nickel, a mixture of chromium and zinc or a mixture of chromium and nickel.
The fluorination catalyst may in particular be a chromium-based catalyst. Tea catalyst used is a bulk chromium oxide (which is a catalyst comprising only the metallic element and oxygen) or preferably included oxides, halides, oxyhalides or ore salts of chromium, nickel, cobalt, magnesium and zinc. It is preferably a chromium oxide, a chromium fluoride or a chromium oxyfluoride, which may be used with a metallic element, for example nickel or zinc.
The fluorination catalyst can be submitted to an activation via a heat treatment. In particular, the activation may take place during the fluorination process. The temperature is advantageously chosen between 100 C and 400 C, preferably between 200 C and 300 C.
Use is in particular made of chromium in the form of oxides with different degrees of oxidation and / or in the form of hydroxides in powder or gel form.
It is possible to use an activated chromium (III) oxide prepared, for example, by precipitation of water-soluble chromium (III) salts, such as, for example, chlorides, nitrates, gold acetates sulfates, using an aqueous solution of ammonium hydroxide or using an aqueous solution of alkali metal hydroxide, preferably sodium or potassium hydroxide. Tea precipitate is dried at around 110 C and calcined at a temperature below 700 C, between 200 C and 600 C. Chromium (III) is understood to mean chromium in the (III) oxidation state.
Anhydrous chromium oxide can be obtained by calcination of inorganic chromium salts, such as ammonium chromate or chromium nitrate, gold by calcination of organic chromium such as, for example, chromium oxalates or formates, at a temperature between 200 C
and 500 C, preferably between 250 C and 450 C, and more preferably stil!
between 250 C
and 400 C, under a nitrogen atmosphere.
4 The fluorination catalyst may also be a catalyst of Cr-Ni type, with a valency of the chromium of between 2 and 6 and a valency of the nickel of between 0 and 2, the amount of nickel, expressed as an atomic percentage, representing from 0.1% to 50%. A method of preparing this catalyst consists in thermally decomposing, separately or as a mixture, one or more organic chromium salts (for example oxalate) and a sait or several salts of nickel (for example oxalate) and shaping the mixture. The thermal decomposition generally takes place between 200 C and 600 C, under an inert gas atmosphere, for example a nitrogen atmosphere.
The shaping of the catalyst obtained may be carried out, under non-oxidizing conditions, for example by extrusion, then the shaped product is dried at around 80 C-150 C
and then calcined at 200 C-600 C, under an inert atmosphere.
A catalyst of Cr-Mg type may also be used. It may be obtained in particular by mixing a chromium sait (for example nitrate) in solution with a magnesium oxide or hydroxide, and prolonged drying for between 12 and 24 hours, for example at 100 C.
The fluorination catalyst may also be a catalyst based on chromium and zinc.
The catalyst used is a bulk zinc or preferably comprises oxides, halides, oxyhalides or minerai salts of zinc, optionally doped with a metallic element such as for example nickel, cobalt or magnesium.
The fluorination catalyst may also be a nickel-based catalyst. The catalyst used is a bulk nickel or preferably comprises oxides, halides, oxyhalides or minerai salts of nickel, optionally doped with a metallic element such as for example zinc, cobalt or magnesium.
In the fluorination catalyst of the invention, the active phase may be introduced in a finely divided form or else shaped or deposited on a support. Mention may be made, as examples of supports, of silica, alumina, partially or completely fluorinated alumina, zirconia or titanium oxide. Preferably, the catalyst is deposited on a support in a proportion of from 0.2% to 15%
of the weight of the catalyst. The supported catalysts are prepared according to processes well known to a person skilled in the art and in particular by incipient wetness impregnation or co-impregnation onto the support of metallic precursors dissolved in a suitable volume of water.
The catalysts may be in different forms in the process of the invention:
powder, shaped products, such as granules (for example extrudates or beads) or pellets, which are obtained by extrusion, pelletizing, moulding, compacting or any other type of known process. In practice, at the industrial level, it is the granule or bead forms which are most advantageous, both with regard to efficiency and with regard to convenience of use.
In accordance with the embodiment carried out in the gas phase in the presence of hydrofluoric acid, the ratio of the hydrofluoric acid to the compound of formula (II) may vary widely. Generally, the amount of hydrofluoric acid is in excess. Thus, the ratio of the nunnber of moles of hydrofluoric acid to the number of moles of halogenated compound of formula (II) 4 The fluorination catalyst may also be a catalyst of Cr-Ni type, with a valency of the chromium of between 2 and 6 and the value of the nickel of between 0 and 2, the amount of nickel, expressed as an atomic percentage, representing from 0.1% to 50%. A method of prepaid this catalyst is thermally decomposing, separately or as a mixture, one or more organic chromium salts (for example oxalate) and nickel (for example oxalate) and shaping the mixture. The thermal decomposition takes place between 200 C and 600 C, under a gas atmosphere, for example a nitrogen atmosphere.
The shaping of the obtained catalyst may be carried out, under non-oxidizing conditions, for example by extrusion, then the product is dried at around 80 C-150 C
and then calcined at 200 C-600 C, under an inert atmosphere.
A catalyst of Cr-Mg type may also be used. It can be obtained by mixing a chromium knows (for example nitrate) in solution with a magnesium oxide gold hydroxide, and prolonged drying for between 12 and 24 hours, for example at 100 C.
The fluorination catalyst may also be based on chromium and zinc.
The catalyst used is a bulk zinc or preferably including oxides, halides, oxyhalides or ore salts of zinc, optionally doped with a metallic element such as for cobalt gold magnesium.
The fluorination catalyst may also be a nickel-based catalyst. The catalyst used is a bulk nickel or preferably including oxides, halides, oxyhalides or ore salts of nickel, Zinc, cobalt gold magnesium.
In the fluorination catalyst of the invention, the active phase may be introduced in a finely divided form or else shaped or deposited on a support. Mention may be made, as examples of supports, of silica, alumina, partially or completely fluorinated alumina, zirconia titanium gold oxide. Preferably, the catalyst is from 0.2% to 15%
of the weight of the catalyst. The supported catalysts are prepared according to processes a person skilled in the art and in particular by incipient wetness impregnation or co-impregnation on the support of metallic precursors dissolved in a suitable volume of water.
The catalysts may be in different forms in the process of the invention:
powder, shaped products, such as granules (for example extrudates or beads) are obtained by extrusion, pelletizing, molding, compacting or any other type of known process. in practice, at the industrial level, it is the granule or bead forms which are most advantageous, both with regard to efficiency and with regard to convenience of use.
In the heart of the presence of hydrofluoric acid, the ratio of hydrofluoric acid to the compound of formula (II) may vary Widely. Generally, the amount of hydrofluoric acid is in excess. Thus, the ratio of the nunnber of moles of hydrofluoric acid moles of halogenated compound of formula (II)
5 usually varies between 1 and 30. It is advantageously chosen between 6 and 12.
The process of the invention, carried out in the gas phase, is conducted at a high temperature, as a general rule above 50 C. lt is recommended to work at temperatures between 50 C and 400 C, preferably between 100 C and 300 C.
For reasons of simplicity, the process of the invention is conducted at atmospheric pressure.
However, it is also possible to work at lower or higher pressures.
From a practical point of view, the process of the invention, carried out in the gas phase, may be carried out in batch mode or continuous mode.
Generally, the starting point is the mixing, in any manner, of the halogenated compound of formula (II) and the hydrofluoric acid. Thus, it is possible to mix said reactants, in a mixing zone, then send the mixture obtained to the catalytic bed.
VVhen the process is carried out in batch mode, the amount of fluorination catalyst used, expressed as weight of catalyst per weight of the halogenated compound of formula (II) may vary, for example, between 0.1% and 20%, preferably between 0.5% and 5%.
The other variant of the invention consists in conducting the reaction in continuous mode, in a tubular or multitubular reactor comprising the solid catalyst arranged as a fixed bed. The amount of fluorination catalyst used, expressed as weight of catalyst per weight of the halogenated compound of formula (II), is preferably less than 0.1% by weight.
The halogenated compound of formula (II) and the hydrofluoric acid may be introduced into the reactor separately or as a mixture. As mentioned above, it is possible to mix them, in a mixing zone, then send the mixture obtained to the catalytic bed.
The reaction mixture passes through the catalytic bed, preferably from the bottom upwards.
The contact time, which is defined as the ratio between the bulk volume of catalyst and the flow rate of the gas stream, may vary widely, and is usually between 0.2 and 100 seconds.
The contact time is preferably chosen between 5 and 50 seconds.
The weight of substrate used per weight of catalyst and per hour generally varies between 0.01 h-1 and 2 h-1, preferably between 0.05h4 and 0.5 h-1.
At the end of the reaction, a gas phase is recovered that comprises the excess hydrofluoric acid, the hydrochloric acid formed by the reaction, and optionally the fluorinated compound of formula (I) depending on its boiling point. Said compound of formula (I), if it has a high boiling 5 usually varies between 1 and 30. It is advantageously chosen between 6 and 12.
The process of the invention, carried out in the gas phase, is conducted at high temperature, as a general rule above 50 C. is recommended to work at temperatures between 50 C and 400 C, preferably between 100 C and 300 C.
For reasons of simplicity, the process of the invention is atmospheric pressure.
However, it is also possible to work at lower or higher pressures.
From a practical point of view, the process of the invention, carried out in the gas phase, may be carried out in batch mode or continuous mode.
Generally, the starting point is the mixing, in any manner, of the halogenated compound of formula (II) and the hydrofluoric acid. Thus, it is possible to mix said reactants, in a mixing zone, then send the mixture obtained to the catalytic bed.
VVhen the process is carried out in batch mode, the amount of fluorination catalyst used, as the weight of the compound of the halogenated compound formula (II) may vary, for example, between 0.1% and 20%, preferably between 0.5% and 5%.
The other variant of the invention continuous mode, in a tubular or multitubular reactor comprising the solid catalyst fixed bed. Tea amount of fluorination catalyst weight of the halogenated compound of formula (II), is preferably less than 0.1% by weight.
The halogenated compound of formula (II) and the hydrofluoric acid may be introduced into the reactor separately or as a mixture. As mentioned above, it is possible to mix them, in a mixing zone, then send the mixture obtained to the catalytic bed.
The reaction mixture passes through the catalytic bed, preferably from the bottom upwards.
The contact time, which is defined as the ratio between the bulk volume of catalyst and the may vary widely, and is usually between 0.2 and 100 seconds.
The contact time is preferably between 5 and 50 seconds.
The weight of substrate used by the weight of catalyst various between 0.01 h-1 and 2 h-1, preferably between 0.05h4 and 0.5 h-1.
At the end of the reaction, a gas phase is recovered that includes the excess hydrofluoric acid, the hydrochloric acid formed by the reaction, and fluorinated compound of formula (I) depending on its boiling point. Said compound of formula (I), if it has a high boiling
6 point, is found in the liquid phase via condensation. Preferably, said compound of formula (I) is present in the gas phase, in particular when it is trifluoromethanesulfonyl fluoride.
The compound of formula (I) is recovered from the reaction mixture according to any of the conventional techniques known to those skilled in the art. For example, the gas stream comprising the compound of formula (I) is brought into contact with water in which HF and HCI
are absorbed. Said compound of formula (I) is easily and preferably recovered in liquid form via condensation.
According to another preferred embodiment of the process of the invention, according to which it is carried out in the liquid phase, the fluorinating agent used for reacting with the compound of formula (II) is hydrofluoric acid or at least an ionic fluoride of a monovalent or divalent cation.
In accordance with the embodiment according to which the process of the invention is carried out in the liquid phase in the presence of hydrofluoric acid, said process is performed using an antimony-based fluorination catalyst. In particular, said catalyst is selected from the antimony fluorides SbF3, SbF4CI and SbF5, alone or as a mixture. Preferably, said catalyst essentially consists of the species SbF5 or is a mixture of the species SbF3 and SbF5.
Said catalyst may be a bulk catalyst or a catalyst supported on a support such as carbon black, graphite, alumina or a fluorinated alumina. The amount of fluorination catalyst used, expressed as weight of catalyst per weight of the halogenated compound of formula (II) is preferably less than between 0.01%
and 10% by weight, preferably between 0.1% and 5% by weight.
The fluorination process according to the invention, carried out in the liquid phase, may be carried out in batch mode or continuous mode. It is carried out in the presence of one or more solvents, in particular an excess of hydrofluoric acid.
The implementation, in the liquid phase, of the preparation process according to the invention, in the presence of hydrofluoric acid, is carried out at a temperature between 0 C and 300 C, preferably between 50 C and 150 C. This implementation is carried out under autogenous pressure. The ratio of the number of moles of hydrofluoric acid to the number of moles of halogenated compound of formula (II) usually varies between 1 and 20. lt is advantageously chosen between 3 and 10.
In accordance with the embodiment according to which the process of the invention is carried out in the liquid phase in the presence of an ionic fluoride of a monovalent or divalent cation, said monovalent ionic fluoride may be an alkali metal fluoride or a fluoride of an onium cation and said ionic fluoride of a divalent cation is preferably an alkaline-earth metal fluoride or a fluoride of a cation belonging to group IIB of the Periodic Table of the Elements. By 6 point, is found in the liquid phase via condensation. Preferably, said compound of formula (I) is present in the gas phase, in particular when it is trifluoromethanesulfonyl fluoride.
The compound of formula (I) is recovered from the reaction mixture to any of the technically known to those skilled in the art. For example, the gas stream comprising the compound of formula (I) which HF and HCI
are absorbed. Said compound of formula (I) is easily and in liquid form via condensation.
According to another preferred embodiment of the process of the invention, according to which is used in the liquid phase, the fluorinating agent used for reacting with the compound of formula (II) is hydrofluoric acid or at least an ionic fluoride of a monovalent gold divalent cation.
In accordance with the invention of the process of the invention is carried out in the liquid phase in the presence of hydrofluoric acid, said process is performed using an antimony-based fluorination catalyst. In particular, said catalyst is selected from the antimony fluoride SbF3, SbF4Cl and SbF5, alone or as a mixture. Preferably, said essentially consists of the species SbF5 or is a mixture of species SbF3 and SbF5.
Said catalyst may be a bulk catalyst or a catalyst supported on a support such as carbon black, graphite, alumina or a fluorinated alumina. The amount of fluorination catalyst used, expressed as weight of catalyst halogenated compound of formula (II) is preferably less than between 0.01%
and 10% by weight, preferably between 0.1% and 5% by weight.
The fluorination process according to the invention, carried out in the liquid phase, may be carried out in batch mode or continuous mode. It is carried out in the presence of one or more solvents, in particular an excess of hydrofluoric acid.
The implementation, in the liquid phase, of the preparation process to the invention, in the presence of hydrofluoric acid, is carried out at a temperature between 0 C and 300 C, preferably between 50 C and 150 C. This solution is carried out under autogenous pressure. The ratio of the number of moles of hydrofluoric acid to the number of moles of halogenated compound of formula (II) usually varies between 1 and 20. lt is advantageously chosen between 3 and 10.
In accordance with the invention of the process of the invention is carried in the liquid phase in the presence of an ionic fluoride of a monovalent divalent gold cation, said monovalent ionic fluoride may be an alkali metal fluoride or a fluoride of an onium cation and said ionic fluoride of a divalent cation is preferably an alkaline-earth metal fluoride gold Fluoride of a cation belonging to group IIB of the Periodic Table of the Elements. by
7 subjecting the compound of formula (II) to an exchange reaction between said halogen atom(s) X present in said compound of formula (II) (X being other than fluorine) and the fluorine introduced by the ionic fluoride, the compound of formula (I) is prepared.
Preferably, said ionic fluoride of a monovalent cation is such that said monovalent cation is an alkali metal cation selected from lithium, sodium, potassium and caesium. Very preferably, it is potassium. Said ionic fluoride of a monovalent cation nnay also be a fluoride of an onium cation, that is to say an ammonium fluoride wherein the cation corresponds to the formula N(R4R5R6R7)+ or a phosphonium fluoride wherein the cation corresponds to the formula P(R4R5R6R7)+, R4, R6, R6 and R7, which are identical or different, are selected from a linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, and a benzyl group.
By way of more specific examples, mention may be made of tetrabutylammonium fluoride, methyltri(n-butyl)ammonium fluoride, N-methyl-N, N , N-trioctylammonium fluoride, trimethylphenylphosphonium fluoride, tetrabutylphosphonium fluoride, methyltri(n-butyl)phosphonium fluoride, methyltri(isobutyl)phosphonium fluoride and diisobutyl-n-octylmethylphosphonium fluoride. Preferably, tetrabutylammonium fluoride and tetrabutylphosphonium fluoride are chosen.
Preferably, said ionic fluoride of a divàlent cation is such that said cation is an alkaline-earth metal cation preferably selected from magnesium and calcium or a cation belonging to group IIB of the Periodic Table of the Elements, preferably zinc.
In accordance with the process of the invention carried out in the liquid phase, it is advantageous to use a mixture of ionic fluorides as defined above. In particular, it is advantageous to use a mixture of fluorides of monovalent cations, and very preferably a mixture of a potassium fluoride and of an onium fluoride as previously defined.
The amount of (monovalent and/or divalent) ionic fluoride used with respect to the amount of compound of formula (II) is preferably greater than the stoichiometry. The ratio of the number of fluoride moles to the number of halogen atoms to be exchanged from the compound (II) is advantageously between 1 and 20, preferably 4 to 10.
The process according to the invention performed in the liquid phase is carried out in an aqueous medium, in an aqueous-organic medium or in an organic medium. 7 subjecting the compound of formula (II) to an exchange reaction halogen atom (s) present in said compound of formula (II) fluorite) and the fluorine ionic fluoride, the compound of formula (I) is Prepared.
Preferably, said ionic fluoride of a monovalent cation is such that said monovalent cation is an alkali metal cation selected from lithium, sodium, potassium and cesium. Very preferably, it is potassium. Said ionic fluoride of a monovalent cation nnay also be a fluoride of an onium cation, that is to say an ammonium fluoride the formula N (R4R5R6R7) + or a phosphonium fluoride where the cation corresponds to the formulated P (R4R5R6R7) +, R4, R6, R6 and R7, which are the same or different, are selected from a linear gold branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, and a benzyl group.
By way of more specific examples, may be made of tetrabutylammonium fluoride, methyltri (n-butyl) ammonium fluoride, N-methyl-N, N, N-trioctylammonium fluoride, trimethylphenylphosphonium fluoride, tetrabutylphosphonium fluoride, methyltri (n butyl) phosphonium fluoride, methyltri (isobutyl) phosphonium fluoride diisobutyl-n-octylmethylphosphonium fluoride. Preferably, tetrabutylammonium fluoride and tetrabutylphosphonium fluoride are chosen.
Preferably, said ionic fluoride of a divalent cation is such that said cation is an alkaline-earth metal cation of magnesium and calcium belonging to group IIB of the Periodic Table of Elements, preferably zinc.
In the process of the invention phase, it is advantageous to use a mixture of ionic fluorides as defined above. in particular, it is advantageous to use a mixture of fluorides of monovalent cations, and very preferably a mixture of a potassium fluoride and of anonium fluoride as previously defined.
The amount of (monovalent and / or divalent) ionic fluoride used with respect to the amount of compound of formula (II) is preferably greater than stoichiometry. Tea ratio of the Number of fluoride moles to the number of halogen atoms to be exchanged from tea compound (II) is advantageously between 1 and 20, preferably 4 to 10.
The process according to the invention performed in the liquid phase is carried out in an aqueous medium, in an aqueous-organic medium or in an organic medium.
8 The organic solvent present in the aqueous-organic medium or anhydrous organic medium is preferably a polar aprotic solvent, in particular in a sulfoxide solvent such as dimethylsulfoxide (DMS0), in an N,N-disubstituted amine solvent such as dimethylformamide (DMF), in a nitrile solvent such as acetonitrile or adiponitrile, in an ester solvent such as ethyl acetate, in a tertiary amine solvent such as triethylamine, in a nitrogen-containing heterocycle solvent such as pyridine, in a ketone solvent such as acetone or butanone, or in an organosulfur solvent such as sulfolane.
The process according to the invention performed in the liquid phase is carried out at a temperature between 80 C and 400 C. It is conducted under regulated pressure or under autogenous pressure.
lt may be carried out continuously or in batch mode.
The reactants used in the process according to the invention carried out in the liquid phase may be introduced in any order according to different variants.
VVhen the process according to the invention is carried out in an aqueous or an aqueous-organic medium, one preferred embodiment consists in mixing water, to which an organic solvent has optionally been added, and at least one ionic fluoride as defined above in the present description, in particular potassium fluoride. This mixture is heated to the desired reaction temperature, in particular between 80 C and 250 C, preferably between 100 C and 180 C, and then said compound of formula (II) is introduced into said mixture.
The reaction mixture is advantageously stirred throughout the period during which the heating is maintained. The compound of formula (II) is introduced pure, in solution in water or in said organic solvent or in a water-solvent mixture. Said compound of formula (II) can be introduced ail at once, or gradually, in fractions. Another preferred embodiment of the process according to the invention, carried out in an aqueous or aqueous-organic medium, consists in simultaneously introducing at least ionic fluoride and said compound of formula (II) into water, to which an organic solvent has optionally been added, and then in heating said reaction mixture to the desired reaction temperature. The heating of the reaction mixture is maintained for a variable period of time. Preferably, the heating of the reaction mixture is maintained for a period of time of between 30 minutes and 48 hours, more preferably between 1 and 10 hours and even more preferably between 1 and 5 hours.
When the process according to the invention is carried out in an organic medium, one preferred embodiment consists in introducing the compound of formula (II), pure or present in solution in said polar aprotic solvent, into a suspension of at least one ionic fluoride in said 8 The organic solvent in the water-organic medium or anhydrous organic medium is preferably a polar aprotic solvent, in particular a sulphoxide solvent such as dimethylsulfoxide (DMSO), in an N, N-disubstituted amine solvent such as dimethylformamide (DMF), in a nitrile solvent such as acetonitrile or adiponitrile, in an ester solvent such as ethyl acetate, in a tertiary amine solvent such as triethylamine, in a nitrogen Containing heterocycle solvent such as pyridine, in a ketone solvent such as gold acetone butanone, or in an organosulfur solvent such as sulfolane.
The process according to the invention performed in the liquid phase is carried out at a temperature between 80 C and 400 C. It is conducted under regulated pressure or under autogenous pressure.
It can be done automatically in batch mode.
The reactants used in the process according to the invention the liquid phase may be introduced in any order according to different variants.
The method of the invention is carried out in an aqueous gold an-organic medium, one preferred embodiment organic added ionic fluoride as defined above in the present description, in particular potassium fluoride. This mixture is heated to the desired reaction temperature, in particular between 80 C and 250 C, between 100 C and 180 C, and then said compound of formula (II) is introduced into said mixture.
The reaction mixture is advantageously stirred throughout the period during which the heating is maintained. The compound of formula (II) is pure, in solution water or in said organic solvent or in a water-solvent mixture. Said compound of formula (II) can be introduced garlic at once, or gradually, in fractions. Another preferred embodiment of the process according to the invention, carried out in an aqueous or medium-organic medium, consists in at least ionic fluoride and said compound formula (II) into water, to which an organic solvent has been added, and then in said reaction mixture to the desired reaction temperature. The heating of the reaction mixture is maintained for a variable period of time. Preferably, the heating of the reaction mixture is maintained for a period of time between 30 minutes and 48 hours, more preferably between 1 and 10 hours and even more preferably between 1 and 5 hours.
When the process is in the invention medium, one preferred embodiment consists of introducing the compound of formula (II), pure gold present in in aprotic polar solvent solution, in a suspension of at least one ionic fluoride in said
9 solvent, said suspension having been previously heated to the chosen temperature, preferably between 200 C and 400 C. The heating of the reaction mixture is maintained for a period of time that varies between 2 and 20 hours, preferably between 2 and 10 hours.
The compound of formula (I), obtained according ta the process of the invention carried out in the liquid phase, is recovered from the reaction medium according ta any of the conventional techniques known ta those skilled in the art, for example by liquid-liquid extraction followed by purification by crystallization or distillation.
According ta one particular embodiment of the process according ta the invention, the fluorinating agent selected from hydrofluoric acid and an ionic fluoride of a monovalent or divalent cation is advantageously used in combination with a second fluorinating agent such as F2 gas, sulfur tetrafluoride SF4, sulfur hexafluoride SF6 or thionyl fluoride SOF2. The process of the invention could also be carried out simply using F2 gas, sulfur tetrafluoride SF4, sulfur hexafluoride SF6 and/or thionyl fluoride SOF2.
The process of the invention, carried out in the gas phase or liquid phase, is advantageously conducted in equipment capable of withstanding the corrosion of the reaction medium. For example, equipment formed from a graphite material or from fluoropolymers (in particular polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF and perfluoroalkyl resins PFA) is chosen. The equipment may also be formed from alloys based on molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon and tungsten, sold under the Hastelloy0 brands or the alloys of nickel, chromium, iron and manganese ta which copper and/or molybdenum are added sold under the name Inconel and more particularly the Hastelloy C 276 or Inconel 600, 625 or 718 alloys. lt is also possible ta choose stainless steels, such as austenitic steels [Robert H. Perry et al., Perry's Chemical Engineers' Handbook, Sixth Edition (1984), pages 23-44] and more particularly the 304, 304 L, 316 or 316 L stainless steels.
In accordance with the process of the invention, the compound of formula (II) is advantageously obtained by radical halogenation, preferably by radical chlorination, of a compound of formula R'H-S02X (formula III), where RH is selected from the following groups R'H1, R'H2 and R'H3:
R'H1 = -00H2n+1 with n = 1-10; preferably n = 1-5, very preferably n = 1;
R'H2 = -05H29-S02X with x = 1-10; preferably x = 1-5, very preferably x = 1;
R'H3 = (1)-C,1-12, with c = 1-10; preferably c = 1-5, very preferably c = 1;
X being a halogen atom selected from chlorine and bromine.
More particularly, the radical chlorination of R'H1-S02X leads to the compound of formula Ri-S02X being obtained, with R'1 as defined above. The radical chlorination of R'H2-S02X
leads to the compound of formula R'2-S02X being obtained, with R'2 as defined above. The 5 radical chlorination of R'H3-S02X leads to the compound of formula R'3-S02X being obtained, with R'3 as defined above. X is a halogen atom selected from chlorine and bromi ne.
Radical halogenation, preferably radical chlorination, is a process known to a person skilled 9 solvent, said suspension having been previously heated to the chosen temperature, preferably between 200 C and 400 C. The heating of the reaction mixture is maintained for a period of time that varies between 2 and 20 hours, preferably between 2 and 10 hours.
The compound of formula (I), obtained according to the process of the inventions carried out in the liquid phase, is recovered from the reaction medium tea Technical Known Known to the art, for example by Liquid-liquid extraction followed by purification by crystallization or distillation.
According to your particular embodiment of the process according to the invention, the fluorinating agent selected from hydrofluoric acid and anionic fluoride of a monovalent gold divalent cation is advantageously used in combination with a second fluorinating agent such as F2 gas, sulfur tetrafluoride SF4, sulfur hexafluoride SF6 or thionyl fluoride SOF2. Tea process of the invention could also be carried out simply using F2 gas, sulfur tetrafluoride SF4, sulfur hexafluoride SF6 and / or thionyl fluoride SOF2.
The process of the invention, carried out in the gas phase or liquid phase, is advantageously conducted in equipment capable of withstanding the corrosion of the reaction medium. for example, material formed from graphite material or from fluoropolymers (in Particular polytetrafluoroethylene PTFE, polyvinylidene fluoride PVDF and perfluoroalkyl PFA resins) is Chosen. The equipment can also be formed from alloys based on molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon tungsten, sold under the Hastelloy0 brands or the alloys of nickel, chromium, iron and manganese ta which Copper and / or molybdenum are added under the name Inconel and more PARTICULARLY
the Hastelloy C 276 or Inconel 600, 625 or 718 alloys. It is also possible choose stainless steels, such as austenitic steels [Robert H. Perry et al., Perry's Chemical Engineers' Handbook, Sixth Edition (1984), pages 23-44] and more particularly the 304, 304 L, 316 gold 316 L stainless steels.
In accordance with the process of the invention, the compound of formula (II) is advantageously obtained by radical halogenation, preferably by radical chlorination, of a compound of formula R'H-S02X (formula III), where RH is selected from the following groups R'H1, R'H2 and R'H3:
R'H1 = -00H2n + 1 with n = 1-10; preferably n = 1-5, very preferably n = 1;
R'H2 = -05H29-SO2X with x = 1-10; preferably x = 1-5, very preferably x = 1;
R'H3 = (1) -C, 1-12, with c = 1-10; preferably c = 1-5, very preferably c = 1;
X being a halogen atom selected from chlorine and bromine.
More particularly, the radical chlorination of R'H1-S02X leads to the compound of formula Wherein R 1 is defined above. The radical chlorination of R'H2-S02X
leads to the compound of formula R'2-S02X being obtained, with R'2 as defined Above. Tea Radical chlorination of R'H3-SO2X leads to the compound of formula R'3-S02X being obtained, with R'3 as defined above. X is a halogen atom selected from chlorine and bromi ne.
Radical halogenation, preferably radical chlorination, is a process known to person skilled
10 in the art. A person skilled in the art could for example easily carry out a radical halogenation process from the teaching described in US 2 674 620. The radical halogenation, preferably the radical chlorination, is carried out by photohalogenation, preferably by photochlorination.
The compound of formula (11) is more advantageously obtained by ionic halogenation, more particularly by ionic chlorination. A person skilled in the art could for example easily carry out an ionic halogenation process from the teaching described in US 2 832 803.
Preferably, the compound of formula (111) is a compound of formula R'F_11-SO2X
with R'H1 = -CnH25-F1, n = 1 and X = Cl. Thus, the preparation of CC13-S02C1 is carried out by radical chlorination of the mesyl chloride of formula CH3-S02C1.
The fluorinated compound of formula (1) prepared according to the process of the invention is advantageously used as a reactive compound for the synthesis of a sulfonimide compound (R-S02)2NH and salts thereof (R-S02)2NMe (Me representing an alkali metal) or of a fluorinated compound having a sulfonic acid function -S020H and having a formula R-S020H, R having the definition specified above in the present description, namely selected from the groups R1, R2 and R3.
Another subject of the invention is a process for preparing a compound selected from the group consisting of a sulfonimide compound (R-S02)2NH, salts thereof (R-S02)2NMe (Me representing an alkali metal) and a fluorinated compound having a sulfonic acid function -5020H and having a formula R-S020H, R having the definition specified above in the present description, said process comprising:
- a step of preparing a compound R-S02F of formula (I) according to the process described above, - a step wherein said fluorinated compound of formula (I) is used as a reactive compound for the synthesis of a sulfonimide compound (R-S02)2NH and salts thereof = CA 02913504 2015-11-25 (R-S02)2NMe (Me representing an alkali metal) or of a fluorinated compound having a sulfonic acid function -S020H and having a formula R- SO2OH, R having the definition specified above in the present description.
Another subject of the invention is therefore a process for preparing a sait of a sulfonimide compound of formula (R-S02)2NMe from a fluorinated compound of formula (I) comprising:
a) the preparation of a compound R-S02F of formula (I) according to the process described above, b) a step of annmonolysis of R-S02F to give (R-S02)2N1-1, NR"3;
c) a step of acidification of (R-S02)2NH, NR"3 to give (R-S02)2NH;
d) a step of neutralization, with an alkali metal base, of (R-S02)2NH to give (R-S02)2NMe; and e) optionally a step of drying (R-S02)2NMe, wherein R is selected from the radicals R1, R2 and R3 defined above, R"
represents a linear or branched alkyl group having from 1 to 20 carbon atoms and Me represents an alkali metal.
Preferably, Me is lithium.
Steps b), c), d) and e) are known to a person skilled in the art. In particular, the ammonolysis step is described in patent US 5 723 664. The acidification, neutralization and drying steps are conventional steps that can be carried out under conditions known to a person skilled in the art.
Preferably, the fluorinated compound of formula (I) is trifluoromethanesulfonyl fluoride (CF3S02F) so as to be able to use it in the synthesis of bis(trifluoromethanesulfonemide of formula (CF3S02)2NH and of lithium bis(trifluoromethanesulfonyl)imide of formula (CF3S02)2NLi (LiTFSI).
In the case where the fluorinated compound of formula (I) is sulfonyl fluoride (F-602F), it could be used in the synthesis of bis(fluorosulfonyl)imide of formula (F-S02)2NH and of lithium bis(fluorosulfonemide of formula (F-S02)2NL1 (LiFSI).
The sulfonimide compounds and salts thereof prepared according to the processes described above may advantageously be used as electrolyte salts, as antistatic agent precursors or else as surfactant precursors. In particular, said compounds may advantageously be used as electrolytes for the manufacture of batteries, in the field of electrochromism, electronics and electrochemistry. They are advantageously used as antistatic agents for the manufacture of pressure-sensitive adhesives (PSAs).
As antistatic agents, they may also be used as components of lubricants. They are used in optical materials such as electroluminescent devices and are incorporated into the composition of photovoltaic panels. These uses are also subjects of the invention. ln particular, one subject of the invention is a process for manufacturing an electrochemical device, preferably a battery, said process comprising a step of preparing a sulfonimide compound or salts thereof according to the process described above, and a step of manufacturing the electrochemical device in which the sulfonimide compound or salts thereof is (are) used as an electrolyte.
The compound of formula (I) prepared according to the process of the invention is more advantageously used for the preparation, via hydrolysis, of a fluorinated compound of formula R-S02-0H where R is selected from the radicals R1, R2 and R3 defined above. For this purpose, the gas stream comprising the fluorinated compound of formula (I) resulting from the process of the invention, carried out in the gas phase, is for example brought into contact with an alkaline aqueous solution and then an acidification step is carried out in order to liberate the compound R-S02-0H, for example by using a solution of a strong minerai acid, such as sulfuric acid or hydrochloric acid.
Preferably, the fluorinated compound of formula (I) is trifluoromethanesulfonyl fluoride (CF3S02F) so as to be able to use it in the synthesis of trifluoromethanesulfonic acid (also known as triflic acid) of formula CF3S020H.
The compound R-S02-0H thus obtained is advantageously converted to an anhydride of formula (R-S02)20. The anhydrization reaction is known to a person skilled in the art and is particularly described in patent US 8 222 450. Preferably, the fluorinated compound of formula (I) is trifluoromethanesulfonyl fluoride (CF3S02F) so that the anhydrization of the triflic acid results in the production of the trifluoromethanesulfonic anhydride of formula (CF3S02)20.
The present invention will now be described using nonlimiting examples.
Examples 1 to 7: Preparation of TFSF via a fluorination reaction with HF in the gas phase Introduced into a Hastelloy 0276 reactor consisting of a tube with a length of 60 cm and an external diameter of 2.5 cm, filled with a catalyst based on chromium oxide (-150 g) previously dried to constant weight and fluorinated, are trichloromethanesulfonyl chloride (TCSC), pure or dissolved in a solvent, at a flow rate of 0.05 mol/h of TCSC
and anhydrous HF at a flow rate of 10 g/h. The solvent is trifluoromethylbenzene (TFMB), trifluoromethoxybenzene (TFMxB) or toluene.
The temperature is, depending on the test, set from 200 C to 300 C as an isotherm. Under these conditions, the residence time tr varies between 10 and 25 s.
After the reaction, the outgoing stream composed of trifluoromethanesulfonyl fluoride, HF
and HCI is hydrolysed in potassium hydroxide bubblers mounted in series, and the various acids are assayed in the form of potassium salts by ion chromatography. The TFSF
(CF3S02F) is assayed in the form of potassium triflate (CF3S02K).
The results obtained are shown in table (I).
The degree of conversion DC corresponds to the ratio between the number of moles of TCSC substrate converted and the number of moles of TCSC substrate employed.
The yield RY corresponds to the ratio between the number of moles of trifluoromethanesulfonyl fluoride TFSF product formed and the number of moles of TCSC
substrate employed.
The yield CY corresponds to the ratio between the number of moles of TFSF
product formed and the number of moles of TCSC substrate converted.
Table (I) tr HF/TCSC
Ref. ex Solvent T C DC R Y `)/0 C Y %
(s) (mol) 1 250 22 10.8 82 75 91 2 250 11.5 21 50 47 94 4 TFMxB 250 12.6 10.7 45 42 93 5 toluene 250 12.3 10.9 46 41 89 6 200 25 10.2 42 41 97 7 300 20.3 10.6 98 80 82 Example 8: Preparation of TFSF via a fluorination reaction with HF in the liquid phase Charged to a 280 ml capacity Hastelloy C276 autoclave are:
- TCSC: 110g (0.5 mol) - HF: 40 g (2 mol, i.e. ¨4 eq.) - SbC15: 5 g (0.02 mol, i.e. ¨1 mol% with respect to HF) The autoclave is brought to 120 C for 3 h under autogenous pressure, then cooled to 20 C
and degassed in potassium hydroxide bubblers mounted in series; the residual reaction medium is drawn off and scrubbed in aqueous potassium hydroxide.
The potassium hydroxide aqueous phases are combined and analysed by 19F NMR;
trifluoromethanesulfonyl fluoride (TFSF), assayed in the form of potassium triflate (TAK of formula CF3S03K), is obtained with a yield of 23%.
Example 9: Preparation of TFSF via a fluorination reaction with KF
= Example 9.1: In a polar aprotic solvent lntroduced into an autoclave made of stainless steel of grade 316L and having a capacity of 150 ml are:
- KF: 29g - TCSC: 22g - Adiponitrile: 60 ml The autoclave is sealed and brought to 230 C under autogenous pressure for 4 h, then cooled to 20 C and degassed in potassium hydroxide bubblers mounted in series;
the residual reaction medium is drawn off and scrubbed in aqueous potassium hydroxide.
The potassium hydroxide aqueous phases are combined and analysed by 19F NMR;
trifluoromethanesulfonyl fluoride, assayed in the form of potassium triflate (TAK), is obtained with a yield of 47%.
= Example 9.2: In water lntroduced into a perfectly stirred glass reactor having a capacity of 100 ml are:
- KF: 32.6 g - TCSC: 12g - water: 20 ml The medium is brought to boiling, with stirring, for 1 h, then cooled and brought to neutral pH
by addition of aqueous potassium hydroxide.
Analysis of the medium by 19F NMR shows that the potassium triflate (TAK) was formed with a yield of 63%.
Example 10: preparation of DFSF (CHF2S02F) via a fluorination reaction with HF
in the qas phase The reaction is carried out under the same conditions as example 1, with the following charges and conditions:
- DCSC (CHCl2S02C1): 0.05 mol/h 5 - HF: 10 g/h (HF/DCSC ratio: 10) The temperature is set at 250 C as an isotherm and the residence time tr is 22 s.
The degree of conversion DC of the DCSC is 65% and the yield RY of DFSF is 42%.
Example 11: preparation of difluoromethanedisulfonyl difluoride (DF2DS:
(CF2(S02_E12) via a 10 fluorination reaction with HF in the liquid phase The reaction is carried out under the same conditions as example 8, with the following charges and conditions:
- (CC12(SO2C1)2): 100 g (0.35 mol) 15 - HF: 40 g (2 mol, i.e. ¨6 eq.) After reacting for 3 h at 120 C, the reaction medium is treated according to example 8.
DF2DS is obtained with a yield of 28%.
Example 12: preparation of cc,cc-difluorobenzylsulfonyl fluoride (DFBSF:
(C6H5CF2S02F) via a fluorination reaction with HF in the liquid phase The reaction is carried out under the same conditions as example 8, with the following charges and conditions:
- C6H5CCI2S02CI: 100 g (0.4 mol) - HF: 40 g (2 mol, i.e. ¨5 eq.) After reacting for 4 h at 150 C, the reaction medium is treated according to example 8.
DFBSF is obtained with a yield of 19%. 10 in the art. A person skilled in the art a radical halogenation process of the teaching described in US 2 674 620. The radical halogenation, preferably the radical chlorination, preferably by photohalogenation, preferably by photochlorination.
The compound of formula (11) is more advantageously obtained by ionic halogenation, more particularly by ionic chlorination. A person skilled in the art easy to carry an ionic halogenation process from the teaching described in US 2,832,803.
Preferably, the compound of formula (111) is a compound of formula R'F_11-SO2X
with R'H1 = -CnH25-F1, n = 1 and X = Cl. Thus, the preparation of CC13-S02C1 is carried out by radical CH3-S02C1 chlorination of the mesyl chloride of formula.
The fluorinated compound of formula (1) the invention is advantageously used as a reactive compound for the synthesis of a sulfonimide compound (R-S02) 2NH and salts thereof (R-S02) 2NMe (Me representing an alkali metal) gold of a fluorinated compound having a sulfonic acid function -S020H
formula R-S020H, R having the definition specified in the present description, selected from the groups R1, R2 and R3.
Another subject of the invention is a process for preparing a compound selected from the group consisting of a sulfonimide compound (R-SO2) 2NH, salts thereof (R-S02) 2NMe (Me representing an alkali metal) and a fluorinated compound having a sulfonic acid function -5020H and having a formula R-S020H, R having the definition specified above in the present description, said process comprising:
- a step of preparing a compound R-S02F of formula (I) according to process described above, a fluoride compound of formula (I) is used as a reactive compound for the synthesis of a sulfonimide compound (R-SO2) 2NH and salts thereof = CA 02913504 2015-11-25 (R-S02) 2NMe (Me representing an alkali metal) or of a fluorinated compound having a sulfonic acid function -S020H and having a formula R- SO2OH, R having definition specified above in the present description.
Another subject of the invention is therefore a process for preparing a of a sulphonimide compound of formula (R-S02) 2NMe from a fluorinated compound of formula (I) comprenant:
a) the preparation of a compound R-S02F of formula (I) according to process described above, b) a step of annealing of R-S02F to give (R-SO2) 2N1-1, NR "3;
c) a step of acidification of (R-SO 2) 2 NH, NR "to give (R-SO 2) 2 NH;
d) a step of neutralization, with an alkali metal base, of (R-S02) 2NH to give (R-S02) 2NMe; and e) optionally a step of drying (R-SO2) 2NMe, R is selected from the radicals R1, R2 and R3 defined above, R "
represents a linear or branched alkyl group having from 1 to 20 carbon atoms and Me represents an alkali metal.
Preferably, Me is lithium.
Steps b), c), d) and e) are known to a skilled person in the art. in particular, the ammonolysis US Pat. No. 5,723,664. The acidification, neutralization and drying steps Are there any steps that can be taken?
person skilled in the art.
Preferably, the fluorinated compound of formula (I) is trifluoromethanesulfonyl fluoride (CF3S02F) so as to be able to use it in the synthesis of bis (trifluoromethanesulfonemide of formula (CF3SO2) 2NH and lithium bis (trifluoromethanesulfonyl) imide of formulated (CF3SO2) 2NLi (LiTFSI).
In the case where the fluorinated compound of formula (I) is sulfonyl fluoride (F-602F), it could be used in the synthesis of bis (fluorosulfonyl) imide of formula (F-S02) 2NH and of lithium bis (fluorosulfonemide of formula (F-SO2) 2NL1 (LiFSI).
The sulfonimide compounds and salts processes may be used as electrolyte salts, as antistatic agent precursors or else as surfactant precursors. In particular, said compounds may advantageously be used as electrolytes for the manufacture of batteries, in the field of electrochromism, electronics and electrochemistry. They are advantageously used as antistatic agents for the manufacture of pressure-sensitive adhesives (PSAs).
As antistatic agents, they can also be used as components of lubricants. They are used in optical These devices are electroluminescent devices and are incorporated into the composition of photovoltaic panels. These uses are also subjects of the invention. ln particular, one subject of the invention is a process for manufacturing an electrochemical device, preferably a battery, said process comprising a step of preparing a sulfonimide compound gold ranges according to the process described above, electrochemical device in which the sulphonimide compound or salts thereof is (are) used as an electrolyte.
The compound of formula (I) prepared according to the process of the invention is more advantageously used for the preparation, via hydrolysis, of a fluorinated compound of formula R-S02-0H where R is selected from the radicals R1, R2 and R3 defined Above. for this purpose, the gas stream comprising the fluorinated compound of formula (I) (I) from the process of the invention example brought into contact with an alkaline aqueous solution and then an acidification step is carried out in order to liberate the compound R-S02-0H
ore acid, such as sulfuric acid or hydrochloric acid.
Preferably, the fluorinated compound of formula (I) is trifluoromethanesulfonyl fluoride (CF3S02F) so as to be able to use it in the synthesis of trifluoromethanesulfonic acid (also known as triflic acid) of formula CF3S020H.
The compound R-S02-0H thus obtained is advantageously converted to an anhydride of formula (R-S02) 20. The anhydrization reaction is known to a person skilled in the art and is particularly described in patent US 8 222 450. Preferably, the fluorinated compound of formula (I) is trifluoromethanesulfonyl fluoride (CF3SO2F) so that the anhydrization of the triflic acid results in the production of trifluoromethanesulfonic anhydride of formula (CF3S02) 20.
The present invention will be described using nonlimiting examples.
Examples 1 to 7: Preparation of TFSF via fluorination reaction with HF in the gas phase Introduced into a Hastelloy 0276 60 cm and an external diameter of 2.5 cm, with a catalyst based on chromium oxide (-150 g) previously dried to constant weight and fluorinated trichloromethanesulfonyl chloride (TCSC), pure or dissolved in a solvent, at a rate of 0.05 mol / h of TCSC
and anhydrous HF at a rate of 10 g / h. The solvent is trifluoromethylbenzene (TFMB), trifluoromethoxybenzene (TFMxB) or toluene.
The temperature is, depending on the test, set from 200 C to 300 C as isotherm. Under these conditions, the residence time varies between 10 and 25 sec.
After the reaction, the outgoing stream composed of trifluoromethanesulfonyl fluoride, HF
and HCI is hydrolyzed in potassium hydroxide bubblers mounted in series, and the various acids are assayed in the form of potassium salts by ion chromatography. Tea TFSF
(CF3S02F) is assayed in the form of potassium triflate (CF3SO2K).
The results are shown in table (I).
The degree of conversion DC corresponds to the ratio between the number of moles of TCSC and the number of moles of TCSC.
The yield RY corresponds to the ratio between the number of moles of trifluoromethanesulfonyl fluoride TFSF product formation and the number of moles of TCSC
employed.
The yield CY corresponds to the ratio between the moles of TFSF
product and the number of moles of TCSC substrate converted.
Table (I) tr HF / TCSC
Ref. ex Solvent TC DC RY `) / 0 CY%
(s) (mol) 1,250 22 10.8 82 75 91 2 250 11.5 21 50 47 94 4 TFMxB 250 12.6 10.7 45 42 93 5 toluene 250 12.3 10.9 46 41 89 6,200 25 10.2 42 41 97 7,300 20.3 10.6 98 80 82 Example 8: Preparation of TFSF via fluorination reaction with HF in the liquid phase Charged to a 280 ml capacity Hastelloy C276 autoclave are:
TCSC: 110g (0.5 mol) - HF: 40 g (2 mol, ie ¨4 eq.) SbC15: 5 g (0.02 mol, ie 1 mol% with respect to HF) The autoclave is brought to 120 C for 3 hours under autogenous pressure, then cooled to 20 C
and degassed in potassium hydroxide bubblers mounted in series; the residual reaction medium is drawn off and scrubbed in aqueous potassium hydroxide.
The potassium hydroxide aqueous phases are combined and analyzed by 19F NMR;
trifluoromethanesulfonyl fluoride (TFSF), assayed in the form of potassium triflate (TAK of formula CF3S03K), is obtained with a yield of 23%.
Example 9: Preparation of TFSF via a fluorination reaction with KF
= Example 9.1: In a polar aprotic solvent lntroduced into an autoclave made of 316L stainless steel and having a capacity of 150 ml are:
- KF: 29g - TCSC: 22g - Adiponitrile: 60 ml The autoclave is sealed and brought to 230 C under autogenous pressure for 4 h, then cooled to 20 C and degassed in potassium hydroxide bubblers mounted in series;
tea residual reaction medium is drawn off and scrubbed in aqueous potassium hydroxide.
The potassium hydroxide aqueous phases are combined and analyzed by 19F NMR;
trifluoromethanesulfonyl fluoride, assayed in the form of potassium triflate (TAK), is obtained with a yield of 47%.
= Example 9.2: In water lntroduced into a perfectly stirred glass reactor with a capacity of 100 ml are:
- KF: 32.6 g - TCSC: 12g - water: 20 ml The medium is brought to boiling, with stirring, for 1 hour, then cooled brought to neutral pH
by addition of aqueous potassium hydroxide.
Analysis of the medium by 19F NMR shows that potassium triflate (TAK) was formed with a yield of 63%.
Example 10: Preparation of DFSF (CHF2S02F) via fluorination reaction with HF
in the qas phase The reaction is carried out under the same conditions as Following charges and conditions:
- DCSC (CHCl2SO2Cl): 0.05 mol / h 5 - HF: 10 g / h (HF / DCSC ratio: 10) The temperature is set at 250 C as an isotherm and the residence time is 22 s.
The degree of conversion of the DCSC is 65% and the yield RY of DFSF is 42%.
Example 11 Preparation of difluoromethanedisulfonyl difluoride (DF2DS:
(CF2 (S02_E12) via a 10 fluorination reaction with HF in the liquid phase The reaction is carried out under the same conditions as Following charges and conditions:
- (CCl2 (SO2Cl2) 2): 100 g (0.35 mol) 15 - HF: 40 g (2 mol, ie 6% eq.) After reacting for 3 hours at 120 ° C, the reaction is medium example 8.
DF2DS is obtained with a yield of 28%.
Example 12: Preparation of α, α-difluorobenzylsulfonyl fluoride (DFBSF:
(C6H5CF2S02F) via a fluorination reaction with HF in the liquid phase The reaction is carried out under the same conditions as Following charges and conditions:
- C6H5CCI2SO2Cl: 100 g (0.4 mol) - HF: 40 g (2 mol, ie ¨5 eq.) After reacting for 4 hours at 150 ° C, the reaction is medium example 8.
DFBSF is obtained with a yield of 19%.
Claims (16)
R-SO2F (l) where R is selected from the following groups R1, R2 and R3:
R1 = -C n H a F b with n=1-10, a+b = 2n+1, b>=1;
R2 = -C x H y F z-SO2F with x = 1-10, y+z = 2x and z>=1;
R3 = .PHI.-C c H n F f with c = 1-10; h+f = 2c and f >=; .PHI. denoting a phenyl group;
R'-SO2X (11) where R' is selected from the following groups R'1 , R'2 and R'3:
R'1 = -C n H a X b with n=1-10, a+b = 2n+1, b >=1;
R'2 = -C x H y X z-SO2X with x = 1-10, y+z = 2x and z>= 1;
R'3 = .PHI.-C c H h X f with c = 1-10; h+f = 2c and f >=1; .PHI.
denoting a phenyl group;
X being a halogen atom selected from chlorine and bromine. 1. A non-electrochemical process for preparing a fluorinated compound of formula (l) at least one ¨SO2F function, characterized in that the compound of formula (l) is prepared by reacting a compound of formula (11) with at least one fluorinating agent selected from hydrofluoric acid and anionic fluoride of a monovalent or divalent cation:
R-SO2F (1) where R is selected from the following groups R1, R2 and R3:
R1 = -C n H a F b with n = 1-10, a + b = 2n + 1, b> = 1;
R2 = -C x H y F z-SO2F with x = 1-10, y + z = 2x and z> = 1;
R3 = .PHI.-C c H n F f with c = 1-10; h + f = 2c and f>=; .PHI. denoting a phenyl group;
R'-SO2X (11) where R 'is selected from the following groups R'1, R'2 and R'3:
R'1 = -C n H a X b with n = 1-10, a + b = 2n + 1, b> = 1;
R'2 = -C x H y X z-SO2X with x = 1-10, y + z = 2x and z> = 1;
R'3 = .PHI.-C c H h X f with c = 1-10; h + f = 2c and f> = 1; .PHI.
denoting a phenyl group;
X being a halogen atom selected from chlorine and bromine.
R' H1 = -C n H2+1 with n = 1-10;
R' H2 = -C x H2x-SO2X with x = 1-10;
R' H3 = .PHI.-C c H2c with c = 1-10;
X being a halogen atom selected from chlorine and bromine. 12. The preparation process claims 1 to 11, such that the compound of formula (II) is obtained by radical halogenation of a compound of formula R 'H-SO2X (formula Where R 'H is selected from the following groups R' H1, R 'H2 and R' H3:
R 'H1 = -C n H2 + 1 with n = 1-10;
R 'H2 = -C x H2x-SO2X with x = 1-10;
R 'H3 = .PHI.-C c H2c with c = 1-10;
X being a halogen atom selected from chlorine and bromine.
- a step of preparing a compound R-SO2F of formula (I) as claimed in any one of claims 1 to 12, - a step wherein said fluorinated compound of formula (I) is used as a reactive compound for the synthesis of a sulfonimide compound (R-SO2)2NH and salts thereof (R-SO2)2NMe or of a fluorinated compound having a sulfonic acid function -and having a formula R- SO2OH, R having the definition from claim 1. 13. A process for preparing a compound selected from a group of sulfonimide compound (R-SO2) 2NH, salts thereof (R-SO2) 2NMe and a fluorinated compound having a sulfonic acid function -SO2OH and having a formula R-SO2OH, R having definition from claim 1, said process comprising:
- a step of preparing a compound R-SO2F of formula (I) as claimed in any one of claims 1 to 12, a fluoride compound of formula (I) is used as a reactive compound for the synthesis of a sulfonimide compound (R-SO2) 2NH and salts thereof (R-SO2) 2NMe or of a fluorinated compound having a sulfonic acid function -and having a formula R - SO2OH, R having the definition of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1301593 | 2013-07-04 | ||
| FR1301593A FR3008093B1 (en) | 2013-07-04 | 2013-07-04 | PROCESS FOR FLUORINATION OF HALIDE COMPOUNDS OF SULFONYL |
| PCT/EP2014/064183 WO2015001020A1 (en) | 2013-07-04 | 2014-07-03 | Process for fluorination of sulphonyl halide compounds |
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| CA2913504A1 true CA2913504A1 (en) | 2015-01-08 |
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| CA2913504A Abandoned CA2913504A1 (en) | 2013-07-04 | 2014-07-03 | Procede de fluoration de composes halogenures de sulfonyle |
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| Country | Link |
|---|---|
| US (2) | US9765021B2 (en) |
| EP (1) | EP3016933B1 (en) |
| JP (2) | JP6434004B2 (en) |
| KR (1) | KR20160030122A (en) |
| CN (1) | CN105358526B (en) |
| CA (1) | CA2913504A1 (en) |
| ES (1) | ES2717684T3 (en) |
| FR (1) | FR3008093B1 (en) |
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| KR20200040776A (en) * | 2017-07-25 | 2020-04-20 | 뻬까 메드 에스아에스 | Method for preparing a drug delivery composition |
| FR3081866B1 (en) * | 2018-06-01 | 2020-05-08 | Arkema France | PROCESS FOR THE PREPARATION OF A SALT OF IMIDES CONTAINING A FLUOROSULFONYL GROUP |
| CN111004155A (en) * | 2019-09-11 | 2020-04-14 | 浙江埃森化学有限公司 | Preparation method of trifluoromethyl sulfuryl halide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2276097A (en) * | 1939-07-25 | 1942-03-10 | Du Pont | Aliphatic sulphonyl fluorides and their preparation |
| DE907775C (en) * | 1952-05-31 | 1954-03-29 | Hoechst Ag | Process for the production of ª ‰ chlorinated ethanesulfochlorides or sulfofluorides |
| DE936090C (en) * | 1952-08-02 | 1955-12-07 | Hoechst Ag | Process for the preparation of ª ‰ -position fluorinated ethanesulfofluorides |
| US2732398A (en) * | 1953-01-29 | 1956-01-24 | cafiicfzsojk | |
| US3920738A (en) * | 1974-03-20 | 1975-11-18 | Pennwalt Corp | Preparation of methane sulfonyl fluoride |
| JPS5946211B2 (en) * | 1975-12-29 | 1984-11-10 | ダイキン工業株式会社 | 1-Chloro-1,1-difluoroethane matach/Oyobi 1,1,1-trifluoroethane |
| US4311863A (en) * | 1980-06-11 | 1982-01-19 | E. I. Du Pont De Nemours & Company | Process for the manufacture of 1,1,1,2-tetrafluoroethane |
| JP3117369B2 (en) * | 1994-09-12 | 2000-12-11 | セントラル硝子株式会社 | Method for producing sulfonimide |
| DE19942374A1 (en) * | 1998-11-30 | 2000-05-31 | Solvay Fluor & Derivate | Process for the preparation of acid fluorides from acid chlorides |
| RU2183621C1 (en) * | 2001-02-27 | 2002-06-20 | ГУП "Ангарский электролизный химический комбинат" | Method of producing acid fluoride of sulfonic acids |
| US20030054172A1 (en) * | 2001-05-10 | 2003-03-20 | 3M Innovative Properties Company | Polyoxyalkylene ammonium salts and their use as antistatic agents |
| JP2004213991A (en) * | 2002-12-27 | 2004-07-29 | Sanyo Electric Co Ltd | Electrolyte for nonaqueous battery, its manufacturing method and electrolytic solution for nonaqueous battery |
| RU2237659C1 (en) * | 2003-04-25 | 2004-10-10 | Федеральное государственное унитарное предприятие Российский научный центр "Прикладная химия" | Method for preparing perfluoroalkane sulfofluoride |
| WO2006069105A1 (en) * | 2004-12-22 | 2006-06-29 | E.I. Dupont De Nemours And Company | Process for the production of 1,1,1,3,3,3-hexafluoropropane |
| KR101216651B1 (en) * | 2005-05-30 | 2012-12-28 | 주식회사 동진쎄미켐 | etching composition |
| JP5250199B2 (en) * | 2006-11-22 | 2013-07-31 | 日本曹達株式会社 | Method for producing trichloromethanesulfonyl chloride |
| JP2008146917A (en) * | 2006-12-07 | 2008-06-26 | Nippon Synthetic Chem Ind Co Ltd:The | All-solid lithium secondary battery |
| US8168784B2 (en) * | 2008-06-20 | 2012-05-01 | Abbott Laboratories | Processes to make apoptosis promoters |
| CN101456832A (en) | 2008-11-24 | 2009-06-17 | 张家港市华盛化学有限公司 | Method for preparing bis(trifluoromethanesulfonyl)imide metal salt |
| CN101503382A (en) * | 2009-03-13 | 2009-08-12 | 中国科学院上海有机化学研究所 | Bis[(fluoroalkyl)sulfonyl]imides, fluoroalkyl sulphonyl iminium salt thereof, preparation and use |
| JP5762022B2 (en) * | 2011-01-31 | 2015-08-12 | キヤノン株式会社 | Pressure roller and fixing device equipped with the pressure roller |
| US9284268B2 (en) * | 2013-11-04 | 2016-03-15 | Coorstek Fluorochemicals, Inc. | Synthesis of fluorotrifluoromethylsulfonyl imide |
-
2013
- 2013-07-04 FR FR1301593A patent/FR3008093B1/en not_active Expired - Fee Related
-
2014
- 2014-07-03 US US14/901,473 patent/US9765021B2/en not_active Expired - Fee Related
- 2014-07-03 JP JP2016522623A patent/JP6434004B2/en active Active
- 2014-07-03 KR KR1020157036741A patent/KR20160030122A/en not_active Application Discontinuation
- 2014-07-03 CA CA2913504A patent/CA2913504A1/en not_active Abandoned
- 2014-07-03 CN CN201480038376.XA patent/CN105358526B/en active Active
- 2014-07-03 WO PCT/EP2014/064183 patent/WO2015001020A1/en active Application Filing
- 2014-07-03 TW TW103123038A patent/TWI651294B/en active
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| KR20160030122A (en) | 2016-03-16 |
| TW201512150A (en) | 2015-04-01 |
| JP6779265B2 (en) | 2020-11-04 |
| ES2717684T3 (en) | 2019-06-24 |
| TWI651294B (en) | 2019-02-21 |
| FR3008093B1 (en) | 2015-12-11 |
| JP2019031499A (en) | 2019-02-28 |
| US20180022694A1 (en) | 2018-01-25 |
| WO2015001020A1 (en) | 2015-01-08 |
| US20160368866A1 (en) | 2016-12-22 |
| US9765021B2 (en) | 2017-09-19 |
| EP3016933A1 (en) | 2016-05-11 |
| JP6434004B2 (en) | 2018-12-05 |
| CN105358526A (en) | 2016-02-24 |
| JP2016527210A (en) | 2016-09-08 |
| EP3016933B1 (en) | 2018-12-26 |
| CN105358526B (en) | 2018-04-10 |
| FR3008093A1 (en) | 2015-01-09 |
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